JP2013112757A - Lithographic ink and printed matter - Google Patents
Lithographic ink and printed matter Download PDFInfo
- Publication number
- JP2013112757A JP2013112757A JP2011260735A JP2011260735A JP2013112757A JP 2013112757 A JP2013112757 A JP 2013112757A JP 2011260735 A JP2011260735 A JP 2011260735A JP 2011260735 A JP2011260735 A JP 2011260735A JP 2013112757 A JP2013112757 A JP 2013112757A
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- resin
- weight
- parts
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 69
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 56
- 239000008158 vegetable oil Substances 0.000 claims abstract description 53
- 239000005011 phenolic resin Substances 0.000 claims abstract description 40
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- 150000002989 phenols Chemical class 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000003208 petroleum Substances 0.000 claims description 36
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- 239000003377 acid catalyst Substances 0.000 claims description 14
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 235000013305 food Nutrition 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 52
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 abstract description 52
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract description 52
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000011134 resol-type phenolic resin Substances 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 79
- 239000002904 solvent Substances 0.000 description 31
- 229920003987 resole Polymers 0.000 description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 22
- 239000008096 xylene Substances 0.000 description 22
- 239000003921 oil Substances 0.000 description 21
- 235000019198 oils Nutrition 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 20
- 235000014113 dietary fatty acids Nutrition 0.000 description 18
- 239000000194 fatty acid Substances 0.000 description 18
- 229930195729 fatty acid Natural products 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000007664 blowing Methods 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- 235000011187 glycerol Nutrition 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000002966 varnish Substances 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- -1 fatty acid ester Chemical class 0.000 description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004945 emulsification Methods 0.000 description 8
- 239000011630 iodine Substances 0.000 description 8
- 229910052740 iodine Inorganic materials 0.000 description 8
- 235000012424 soybean oil Nutrition 0.000 description 8
- 239000003549 soybean oil Substances 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 7
- 239000000944 linseed oil Substances 0.000 description 7
- 235000021388 linseed oil Nutrition 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000003349 gelling agent Substances 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DWANEFRJKWXRSG-UHFFFAOYSA-N 1,2-tetradecanediol Chemical compound CCCCCCCCCCCCC(O)CO DWANEFRJKWXRSG-UHFFFAOYSA-N 0.000 description 2
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000005733 Raphanus sativus var niger Nutrition 0.000 description 2
- 235000019485 Safflower oil Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000005713 safflower oil Nutrition 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- 229940031723 1,2-octanediol Drugs 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- HBFHSDDGEBQGKK-UHFFFAOYSA-N 2,2,4,4-tetramethylpentane-1,1-diol Chemical compound CC(C)(C)CC(C)(C)C(O)O HBFHSDDGEBQGKK-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- ZWNMRZQYWRLGMM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diol Chemical compound CC(C)(O)CCC(C)(C)O ZWNMRZQYWRLGMM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- JFMYRCRXYIIGBB-UHFFFAOYSA-N 2-[(2,4-dichlorophenyl)diazenyl]-n-[4-[4-[[2-[(2,4-dichlorophenyl)diazenyl]-3-oxobutanoyl]amino]-3-methylphenyl]-2-methylphenyl]-3-oxobutanamide Chemical compound C=1C=C(C=2C=C(C)C(NC(=O)C(N=NC=3C(=CC(Cl)=CC=3)Cl)C(C)=O)=CC=2)C=C(C)C=1NC(=O)C(C(=O)C)N=NC1=CC=C(Cl)C=C1Cl JFMYRCRXYIIGBB-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- HHKAGFTWEFVXET-UHFFFAOYSA-N 2-heptyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCCCCCCC(CO)(CO)CO HHKAGFTWEFVXET-UHFFFAOYSA-N 0.000 description 1
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
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- KSNKQSPJFRQSEI-UHFFFAOYSA-N 3,3,3-trifluoropropanoic acid Chemical compound OC(=O)CC(F)(F)F KSNKQSPJFRQSEI-UHFFFAOYSA-N 0.000 description 1
- AHHQDHCTHYTBSV-UHFFFAOYSA-N 3-methylpentane-1,3,5-triol Chemical compound OCCC(O)(C)CCO AHHQDHCTHYTBSV-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- DWDURZSYQTXVIN-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]aniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 DWDURZSYQTXVIN-UHFFFAOYSA-N 0.000 description 1
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- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- 229910015900 BF3 Inorganic materials 0.000 description 1
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
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- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 1
- 239000004233 Indanthrene blue RS Substances 0.000 description 1
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
本発明は、書籍、チラシ、カタログ、新聞等の印刷物に使用される平版印刷インキ（以下、「インキ」と略す。）に使用する樹脂に関することであり、特に乳化抑制機能が高く、印刷時の汚れを軽減することを特徴とするロジン変性フェノール樹脂に関するものである。 The present invention relates to a resin used for a lithographic printing ink (hereinafter abbreviated as “ink”) used for printed matter such as books, leaflets, catalogs, newspapers, etc., and has a particularly high emulsification suppression function and is suitable for printing. The present invention relates to a rosin-modified phenolic resin characterized by reducing dirt.
平版印刷インキは５〜１００Ｐａ・ｓの比較的粘度の高いインキである。平版印刷機の機構は、インキが印刷機のインキ壺から複数のローラーを経由して版面の画線部に供給され、湿し水を使用する平版印刷では非画線部に湿し水が供給され、湿し水無し平版印刷では非画線部がシリコン層でできておりインキを反発し紙上に画像が形成される。 The lithographic printing ink is an ink having a relatively high viscosity of 5 to 100 Pa · s. The mechanism of the lithographic printing machine is such that ink is supplied from the ink fountain of the printing machine to the image line area of the printing plate via multiple rollers, and in lithographic printing using dampening water, dampening water is supplied to the non-image area area. In lithographic printing without dampening water, the non-image area is made of a silicon layer, and the ink is repelled to form an image on the paper.
特に、湿し水を使用した平版印刷においてはインキと湿し水との乳化バランスが重要であり、インキにおいても耐乳化性の高速印刷適性が求められている。インキは乳化量が高過ぎると非画線部にもインキが着肉し易くなり汚れが発生し、乳化量が少ないと絵柄の少ない印刷時には、インキ表面に湿し水が吐き出される為、ロール間のインキ転移や用紙へのインキ着肉性が悪くなり、安定して印刷する事が難しくなる。 In particular, in lithographic printing using a fountain solution, the emulsification balance between the ink and the fountain solution is important, and the ink is also required to have high emulsification resistance and high-speed printability. If the amount of emulsified ink is too high, the ink will easily deposit on non-image areas and stains will occur. If the amount of emulsified is small, dampening water will be sprinkled on the ink surface when printing with a small pattern, so that Ink transfer and ink inking onto paper deteriorate, making it difficult to print stably.
さらに近年では、印刷時の省人、省力化、自動化、高速化の要求が高まってきており、特に印刷スピードは益々高速化してきている。そして、様々な印刷条件下に於いてトラブルレスで長時間安定して高品位な印刷物が得られる印刷用インキが望まれており、インキメーカーでは種々の改良を実施してきている。 Furthermore, in recent years, demands for labor saving, labor saving, automation, and high speed during printing have increased, and in particular, the printing speed has been increasingly increased. In addition, there is a demand for a printing ink that can obtain a high-quality printed matter stably for a long time without any trouble under various printing conditions, and ink manufacturers have made various improvements.
高品位な印刷物が得られる印刷用インキとして、特に要望されているのが、高光沢インキである。 Highly glossy inks are particularly desired as printing inks that can provide high-quality printed matter.
従来、印刷物の光沢を向上させる方法としては、石油系溶剤や植物油などを増やし、インキの粘度を下げて印刷表面の平滑性を向上させたり、低分子高溶解樹脂や石油樹脂などを使用してインキ系内の樹脂成分を増やすことによって、印刷紙へのインキの浸透を極力抑制してインキ被膜厚を維持させるなどの方法が用いられてきた。 Conventionally, as a method of improving the gloss of printed matter, increase the petroleum solvent and vegetable oil, etc., reduce the viscosity of the ink to improve the smoothness of the printing surface, or use low molecular weight highly soluble resin or petroleum resin, etc. By increasing the resin component in the ink system, a method has been used in which the ink film thickness is maintained by suppressing the penetration of the ink into the printing paper as much as possible.
しかしながら、インキ粘度を下げるために石油系溶剤や植物油を増やすと、インキのタック値が低下し、印刷機上でのローラー間転移が悪化する傾向にある。また、低分子高溶解樹脂や石油樹脂などを使用してインキ系内の樹脂成分を増やす処方は、インキのタック値が上がりすぎ、紙剥けが発生したり、乳化の制御が困難となりインキの印刷適性が阻害され、印刷適性を維持しながら印刷物の光沢を向上させるには限界があった。 However, when petroleum-based solvents and vegetable oils are increased in order to reduce the ink viscosity, the tack value of the ink is lowered, and the transition between rollers on the printing press tends to deteriorate. In addition, formulations that increase the resin component in the ink system using low-molecular high-solubility resins, petroleum resins, etc., increase the tack value of the ink, causing paper peeling, making it difficult to control emulsification, and printing the ink. Suitability was hindered, and there was a limit to improving the gloss of printed matter while maintaining printability.
上記の方法以外に、インキ系内の樹脂成分に対する溶解性が高い部類の石油系溶剤を用いることでインキ系内の相溶性を上げてインキの低粘度化や樹脂成分の高濃度化を図る方法もある。しかしながら、上記の石油系溶剤の樹脂に対する溶解性では光沢効果が十分に得られない。また、上記の石油系溶剤の多くは、人体への悪影響の大きい芳香族炭化水素が主成分であり、印刷において、印刷作業環境や大気汚染などの環境負荷の要因となることから、最近では使用を見合わせている。 In addition to the above method, a method of increasing the compatibility in the ink system by using a class of petroleum-based solvent that is highly soluble in the resin component in the ink system, thereby reducing the viscosity of the ink and increasing the concentration of the resin component There is also. However, the gloss effect cannot be sufficiently obtained by the solubility of the above petroleum-based solvent in the resin. In addition, most of the above petroleum-based solvents are mainly composed of aromatic hydrocarbons, which have a large adverse effect on the human body, and they have recently been used in printing due to environmental impacts such as the printing work environment and air pollution. I have forgotten.
また、インキ中に脂肪酸エステルを含有させることで、光沢の優れたオフセットインキ組成物が開発されている（特許文献１、２）。しかしながら、これらの方法では、脂肪酸エステルの紙への浸透制御が困難であり、印刷時に使用される用紙に制限が加えられたり、インキの乾燥性の点で十分満足できない状況がある。 Moreover, the offset ink composition excellent in gloss is developed by containing fatty acid ester in ink (patent documents 1, 2). However, in these methods, it is difficult to control the permeation of fatty acid ester into the paper, and there are situations where the paper used at the time of printing is restricted and the ink drying property is not satisfactory.
インキに使用されるロジン変性フェノール樹脂についての改良も行われてきた。特許文献３では、ロジンと動植物油脂肪酸との混合物をモノアルコールで部分エステル化したモノエステル体に、多価アルコールおよびフェノールホルムアルデヒド初期縮合物を反応させる方法が公開されている。しかしながら、この方法では、エステル化にモノアルコールを使用することで、ロジンおよび動植物油脂肪酸とのエステル結合による架橋が行われず、分子量制御が困難となる。 Improvements have also been made to rosin modified phenolic resins used in inks. Patent Document 3 discloses a method in which a polyester and a phenol formaldehyde initial condensate are reacted with a monoester obtained by partially esterifying a mixture of rosin and animal and vegetable oil fatty acids with monoalcohol. However, in this method, by using monoalcohol for esterification, crosslinking by rosin and animal and vegetable oil fatty acid by an ester bond is not performed, and thus molecular weight control becomes difficult.
また、特許文献４では、レゾ−ル型フェノール類・ホルムアルデヒド初期縮合物、ヨウ素価１００以上の植物油、ロジン、多価アルコ−ルなどを反応させて得られる油変性ロジンフェノール樹脂が開示されており、特許文献５では、フェノール類、ホルムアルデヒド、ヨウ素価１００以上の動植物油、ロジン、１価アルコ−ルおよび／または多価アルコ−ルなどを反応させて得られる油変性ロジンフェノール樹脂が開示されている。しかしながら、食用に用いられるバージンの植物油を用いることは、環境対応の観点から好ましくない。 Further, Patent Document 4 discloses an oil-modified rosin phenol resin obtained by reacting a resole type phenol / formaldehyde initial condensate, vegetable oil having an iodine value of 100 or more, rosin, polyhydric alcohol and the like. Patent Document 5 discloses an oil-modified rosin phenol resin obtained by reacting phenols, formaldehyde, animal and vegetable oils having an iodine value of 100 or more, rosin, monovalent alcohol, and / or polyhydric alcohol. Yes. However, the use of virgin vegetable oil used for food is not preferable from the viewpoint of environmental friendliness.
ロジン変性フェノール樹脂に用いられるフェノール樹脂は、レゾール型とノボラック型の２つの種類がある。アルカリ性触媒を用いることにより、ロジンへの反応性のメチロール基を有するレゾール型フェノール樹脂が得られ、酸性触媒を用いることにより、反応性基を有しないノボラック型フェノール樹脂が得られるものである。ロジン変性フェノール樹脂の石油系溶剤への溶解性を向上させる試みとして、フェノール類のノボラック化を先ず行ない、次いでレゾール化する方法で製造されたノボラック・レゾール型フェノール樹脂を用いてロジン変性フェノール樹脂を製造する方法が、特許文献５に開示されている。当該特許文献の実施例では、ロジン１００重量部に対して、フェノール樹脂１５０から１６２．５重量部のフェノール樹脂を反応させてなるロジン変性フェノール樹脂が開示されている。 There are two types of phenolic resins used for rosin-modified phenolic resins: resol type and novolac type. By using an alkaline catalyst, a resol type phenol resin having a methylol group reactive to rosin can be obtained, and by using an acidic catalyst, a novolak type phenol resin having no reactive group can be obtained. In an attempt to improve the solubility of rosin-modified phenolic resins in petroleum-based solvents, rosin-modified phenolic resins were prepared using a novolak-resole-type phenolic resin produced by first performing novolacization of phenols and then resolubilizing. A manufacturing method is disclosed in Patent Document 5. In the examples of this patent document, a rosin-modified phenol resin obtained by reacting phenol resin 150 to 162.5 parts by weight with 100 parts by weight of rosin is disclosed.
長時間印刷時においても、地汚れを低減させ、光沢感のある高品質の印刷物を得ることが出来る、平版印刷インキ用樹脂およびそれを含有させた平版印刷インキの提供を目的とする。 An object of the present invention is to provide a resin for a lithographic printing ink and a lithographic printing ink containing the same, which can reduce background stains and obtain a glossy and high-quality printed matter even during long-time printing.
上記課題を解決するために誠意研究した結果、以下に定める素材により作製したロジン変性フェノール樹脂を含有させた平版印刷インキは、インキの流動性および印刷物の光沢性に優れていることを見出し、本発明を完成するに至った。 As a result of sincere research to solve the above problems, it was found that a lithographic printing ink containing a rosin-modified phenolic resin produced with the following materials is excellent in ink fluidity and gloss of printed matter. The invention has been completed.
すなわち、本発明の第１の発明は、ロジン類（ａ）、レゾール型フェノール樹脂（ｂ）、再生処理した植物油（ｃ）およびポリオール（ｄ）を酸触媒下で反応させてなることを特徴とするロジン変性フェノール樹脂（Ａ）の製造方法に関するものである。 That is, the first invention of the present invention is characterized by reacting rosins (a), resol type phenol resin (b), regenerated vegetable oil (c) and polyol (d) in the presence of an acid catalyst. The present invention relates to a method for producing a rosin-modified phenolic resin (A).
さらに、本発明の第２の発明は、ロジン変性フェノール樹脂（Ａ）が、重量固形分比で、ロジン類（ａ）５〜７５重量％、レゾール型フェノール樹脂（ｂ）１５〜８５重量％、再生処理した植物油（ｃ）５〜３０重量％およびポリオール（ｄ）０〜２０重量％を酸触媒下で反応させてなることを特徴とする第１の発明記載のロジン変性フェノール樹脂（Ａ）の製造方法に関するものである。 Further, according to a second aspect of the present invention, the rosin-modified phenol resin (A) is a rosin (a) of 5 to 75% by weight, a resol type phenol resin (b) of 15 to 85% by weight, The rosin-modified phenolic resin (A) according to the first invention, which is obtained by reacting 5 to 30% by weight of the regenerated vegetable oil (c) and 0 to 20% by weight of the polyol (d) in the presence of an acid catalyst. It relates to a manufacturing method.
また、本発明の第３の発明は、ロジン変性フェノール樹脂（Ａ）が、重量固形分比で、ロジン類（ａ）５〜７５重量％、レゾール型フェノール樹脂（ｂ）１５〜８５重量％、再生処理した植物油（ｃ）５〜３０重量％、ポリオール（ｄ）０〜２０重量％および石油樹脂（ｅ）５〜３０重量％を酸触媒下で反応させてなることを特徴とする第１の発明または第２の発明記載のロジン変性フェノール樹脂（Ａ）の製造方法に関するものである。 In the third invention of the present invention, the rosin-modified phenolic resin (A) has a weight to solid content ratio of rosins (a) of 5 to 75% by weight, resol type phenolic resin (b) of 15 to 85% by weight, Regenerated vegetable oil (c) 5-30% by weight, polyol (d) 0-20% by weight and petroleum resin (e) 5-30% by weight are reacted in the presence of an acid catalyst. The present invention relates to a method for producing a rosin-modified phenolic resin (A) described in the second invention.
さらに、本発明の第４の発明は、再生処理した植物油（ｃ）が、飲食物の製造に用いた植物油を再生処理した植物油であることを特徴とする第１の発明ないし第３の発明いずれか記載のロジン変性フェノール樹脂（Ａ）の製造方法に関するものである。 Furthermore, the fourth invention of the present invention is any one of the first to third inventions, characterized in that the regenerated vegetable oil (c) is a regenerated vegetable oil used in the production of food and drink. This invention relates to a method for producing the rosin-modified phenolic resin (A).
また、本発明の第５の発明は、第１の発明ないし第４の発明いずれか記載の製造方法により合成させてなることを特徴とするロジン変性フェノール樹脂（Ａ）に関するものである。 The fifth invention of the present invention relates to a rosin-modified phenolic resin (A) characterized by being synthesized by the production method according to any one of the first to fourth inventions.
さらに、本発明の第６の発明は、第５の発明記載のロジン変性フェノール樹脂（Ａ）を含有することを特徴とする平版印刷インキに関するものである。 Furthermore, the sixth invention of the present invention relates to a lithographic printing ink comprising the rosin-modified phenol resin (A) described in the fifth invention.
また、本発明の第７の発明は、第６の発明記載の平版印刷インキを印刷してなる印刷物に関するものである。 The seventh invention of the present invention relates to a printed matter obtained by printing the planographic printing ink described in the sixth invention.
本発明は、再生処理した植物油を反応してなるロジン変性フェノール樹脂を含有する印刷インキを使用することで、環境対策がなされ、且つ、酸触媒下で反応してなるロジン変性フェノール樹脂を含有する印刷インキを使用することで、様々な条件下で印刷時の地汚れを軽減させ長時間安定した印刷が可能で、光沢感のある高品質の印刷物を得ることが出来る印刷インキ用組成物の合成方法並びにそれを用いたインキの提供を目的とする。 The present invention uses a printing ink containing a rosin-modified phenolic resin obtained by reacting a regenerated treated vegetable oil, and contains a rosin-modified phenolic resin that is environmentally friendly and reacts in the presence of an acid catalyst. By using printing ink, synthesis of a composition for printing ink that can reduce scumming during printing under various conditions, enable stable printing for a long time, and obtain a high-quality print with a glossy feeling. It is an object to provide a method and an ink using the method.
まず、本発明のロジン類（ａ）について説明する。 First, the rosins (a) of the present invention will be described.
本発明のロジン類（ａ）としては、ガムロジン、トール油ロジン、ウッドロジンなどの天然ロジン、該天然ロジンから誘導される重合ロジン、天然ロジンや重合ロジンを不均化または水素添加して得られる安定化ロジン、天然ロジンや重合ロジンに不飽和カルボン酸類を付加して得られる不飽和酸変性ロジンなどが上げられる。なお、不飽和酸変性ロジンとは、例えばマレイン酸変性ロジン、無水マレイン酸変性ロジン、フマル酸変性ロジン、イタコン酸変性ロジン、クロトン酸変性ロジン、ケイ皮酸変性ロジン、アクリル酸変性ロジン、メタクリル酸変性ロジンなど、またはこれらに対応する酸変性重合ロジンがあげられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。 The rosins (a) of the present invention include natural rosins such as gum rosin, tall oil rosin and wood rosin, polymerized rosin derived from the natural rosin, and stable products obtained by disproportionating or hydrogenating natural rosin and polymerized rosin. And an unsaturated acid-modified rosin obtained by adding an unsaturated carboxylic acid to a natural rosin or a polymerized rosin. The unsaturated acid-modified rosin is, for example, maleic acid-modified rosin, maleic anhydride-modified rosin, fumaric acid-modified rosin, itaconic acid-modified rosin, crotonic acid-modified rosin, cinnamic acid-modified rosin, acrylic acid-modified rosin, methacrylic acid Examples thereof include modified rosin and acid-modified polymerized rosin corresponding thereto. These may be used alone or in combination of two or more.
本発明のレゾール型フェノール樹脂（ｂ）は、常法により得ることが出来る。合成方法の一例としては、フェノール類（Ｐ）とアルデヒド類（Ｆ）を仕込み、揮発性有機溶剤（キシレンなど）を添加し、金属酸化物触媒またはアルカリ触媒存在下で縮合反応させることにより得られる。フェノール類（Ｐ）とアルデヒド類（Ｆ）の比率（Ｐ／Ｆ）が通常ｍｏｌ比で、１．０〜４．０が好ましく、更に好ましくは１．５〜３．０であり、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化リチウム等の金属水酸化物触媒の存在下または、有機アミンなどのアルカリ触媒の存在下で常圧または加圧下で付加・縮合して得られる各種公知の縮合物が用いられる。フェノール類としては、フェノール水酸基を持つすべての芳香族化合物が使用でき、石炭酸、クレゾール、アミルフェノール、ビスフェノールＡ、ｐ−ブチルフェノール、ｐ−オクチルフェノール、ｐ−ノニルフェノール、ｐ−ドデシルフェノール等が挙げられるが、中でもアルキル置換したフェノール類が好ましい。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。アルデヒド類としては、ホルムアルデヒド、パラホルムアルデヒド等があげられる。 The resol type phenol resin (b) of the present invention can be obtained by a conventional method. As an example of the synthesis method, it is obtained by adding phenols (P) and aldehydes (F), adding a volatile organic solvent (such as xylene), and performing a condensation reaction in the presence of a metal oxide catalyst or an alkali catalyst. . The ratio (P / F) of phenols (P) to aldehydes (F) is usually a molar ratio, preferably 1.0 to 4.0, more preferably 1.5 to 3.0, sodium hydroxide , Various known products obtained by addition / condensation in the presence of a metal hydroxide catalyst such as potassium hydroxide, calcium hydroxide or lithium hydroxide or in the presence of an alkali catalyst such as an organic amine under normal pressure or pressure. A condensate is used. As the phenols, all aromatic compounds having a phenol hydroxyl group can be used, and examples thereof include carboxylic acid, cresol, amylphenol, bisphenol A, p-butylphenol, p-octylphenol, p-nonylphenol, and p-dodecylphenol. Of these, alkyl-substituted phenols are preferred. These may be used alone or in combination of two or more. Examples of aldehydes include formaldehyde and paraformaldehyde.
本発明における再生処理した植物油（ｃ）とは、回収、再生処理された植物油ものことである。再生植物油としては、含水率を０．３重量％以下、ヨウ素価を９０以上、酸価を３以下として再生処理した油が好ましく、より好ましくはヨウ素価１００以上である。含水率を０．３重量％以下にすることにより水分に含まれる塩分等のインキの乳化挙動に影響を与える不純物を除去することが可能となり、ヨウ素価を９０以上として再生することにより、乾燥性、すなわち酸化重合性の良いものとすることが可能となり、さらに酸価が３以下の植物油を選別して再生することにより、インキの過乳化を抑制することが可能となる。回収植物油の再生処理方法としては、濾過、静置による沈殿物の除去、および活性白土等による脱色といった方法が挙げられるが、これらに限定されるものではない。 The regenerated vegetable oil (c) in the present invention is a vegetable oil that has been recovered and regenerated. The regenerated vegetable oil is preferably an oil regenerated with a water content of 0.3% by weight or less, an iodine value of 90 or more, and an acid value of 3 or less, more preferably an iodine value of 100 or more. By making the moisture content 0.3% by weight or less, it becomes possible to remove impurities that affect the emulsification behavior of the ink, such as salt contained in moisture, and by regenerating with an iodine value of 90 or more, drying properties That is, it becomes possible to make it good in oxidative polymerizability, and it becomes possible to suppress over-emulsification of ink by selecting and regenerating vegetable oil having an acid value of 3 or less. Examples of the method for regenerating the recovered vegetable oil include, but are not limited to, filtration, removal of precipitates by standing, and decolorization by activated clay.
再生植物油に用いられるバージンの植物油とは、グリセリンと脂肪酸とのトリグリセリライドにおいて、少なくとも１つの脂肪酸が、炭素−炭素不飽和結合を少なくとも１つ有する脂肪酸であるトリグリセリライドである。例として、アサ実油、アマニ油、エノ油、オイチシカ油、オリーブ油、カカオ油、カポック油、カヤ油、カラシ油、キョウニン油、キリ油、ククイ油、クルミ油、ケシ油、ゴマ油、サフラワー油、ダイコン種油、大豆油、大風子油、ツバキ油、トウモロコシ油、ナタネ油、ニガー油、ヌカ油、パーム油、ヒマシ油、ヒマワリ油、ブドウ種子油、ヘントウ油、松種子油、綿実油、ヤシ油、落花生油、脱水ヒマシ油等が挙げられる。本発明において、さらに好適な植物油を挙げるとすれば、そのヨウ素価が少なくとも９０以上である植物油が好ましく、さらにヨウ素価が１００以上の植物油がより好ましい。ヨウ素価を１００以上とすることで、植物油分子中の反応点が増し、高分子量化に有利となる。 The virgin vegetable oil used in the regenerated vegetable oil is triglyceride in which at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond in triglyceride of glycerin and fatty acid. Examples are: Asa seed oil, flaxseed oil, eno oil, prickly oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil , Japanese radish seed oil, soybean oil, daikon oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil, cottonseed oil, palm Oil, peanut oil, dehydrated castor oil, and the like. In the present invention, a more preferred vegetable oil is preferably a vegetable oil having an iodine value of at least 90, more preferably a vegetable oil having an iodine value of 100 or more. By setting the iodine value to 100 or more, the reaction point in the vegetable oil molecule increases, which is advantageous for increasing the molecular weight.
本発明における酸触媒とはベンゼンスルホン酸、ｐ−トルエンスルホン酸、ｐ−ドデシルベンゼンスルホン酸、メタンスルホン酸、エタンスルホン酸等の有機スルホン酸類、硫酸、塩酸等の鉱酸、トリフルオロメチル硫酸、トリフルオロメチル酢酸等が例示できる。 The acid catalyst in the present invention is benzenesulfonic acid, p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, organic sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, trifluoromethyl sulfuric acid, Examples thereof include trifluoromethyl acetic acid.
本発明では、インキの乳化を抑制させるため、酸触媒を使用することができる。酸触媒については、全樹脂中０．０１〜５重量％の範囲で使用するのが好ましい。０．０１重量％未満、５重量％を上回ると、インキに必要な樹脂粘度および弾性を得ることができない。酸触媒はエステル化反応中にロジン類（ａ）のカルボキシル基を脱炭酸反応により消滅させるため極性を低下させ、これがインキの乳化抑制に効果を発揮していると考えられる。 In the present invention, an acid catalyst can be used to suppress emulsification of the ink. The acid catalyst is preferably used in the range of 0.01 to 5% by weight in the total resin. If it is less than 0.01% by weight and exceeds 5% by weight, the resin viscosity and elasticity required for the ink cannot be obtained. It is considered that the acid catalyst reduces the polarity because the carboxyl group of the rosins (a) disappears by the decarboxylation reaction during the esterification reaction, and this is considered to be effective in suppressing the emulsification of the ink.
本発明において使用される石油樹脂（ｅ）の成分としては、ナフサを分解した際の炭素数の多い不飽和化合物を重合したものであり、Ｃ５留分を原料とする脂肪族系、Ｃ９留分を原料とする芳香族系、シクロペンタジエン（ジシクロペンタジエン）を原料とする脂環族系、さらにＣ５留分とＣ９留分を原料とした共重合系があり、重量平均分子量が５００〜１０００００ 程度のものが一般的である。Ｃ５留分としては、イソプレン、ピペリレン、シクロペンタジエン、ペンテン類、ペンタン類等、Ｃ９留分としては、ビニルトルエン、インデン、ジシクロペンタジエン等が挙げられ、それぞれ触媒の存在下あるいは無触媒で熱重合して得られるものである。触媒としてはフリーデルクラフト型のルイス酸触媒、例えば三フッ化ホウ素およびそのフェノール、エーテル、酢酸等との錯体が通常使用される。アリルアルコール、酢酸ビニルエステル等を共重合して得ることも可能であるし、得られた石油樹脂に無水マレイン酸、アクリル酸等を付加することも可能である。 As a component of the petroleum resin (e) used in the present invention, an aliphatic compound obtained by polymerizing an unsaturated compound having a large number of carbon atoms when naphtha is decomposed, an aliphatic system using a C5 fraction as a raw material, a C9 fraction There is an aromatic system using as raw material, an alicyclic system using cyclopentadiene (dicyclopentadiene) as a raw material, and a copolymer system using C5 and C9 fractions as raw materials, and the weight average molecular weight is about 500 to 100,000. The ones are common. Examples of the C5 fraction include isoprene, piperylene, cyclopentadiene, pentenes, and pentanes. Examples of the C9 fraction include vinyltoluene, indene, and dicyclopentadiene. Thermal polymerization is performed in the presence of a catalyst or without catalyst. Is obtained. As the catalyst, Friedel-Craft type Lewis acid catalyst such as boron trifluoride and its complex with phenol, ether, acetic acid and the like are usually used. It can be obtained by copolymerizing allyl alcohol, vinyl acetate or the like, and maleic anhydride, acrylic acid or the like can be added to the obtained petroleum resin.
上記石油樹脂は市販のものを適宜使用することが可能であり、脂肪族系石油樹脂としては、日本ゼオン社製クイントンＡ１００、クイントンＢ１７０、クイントンＫ１００、クイントンＭ１００、クイントンＲ１００、クイントンＣ２００Ｓ、丸善石油化学社製マルカレッツＴ−１００ＡＳ、マルカレッツＲ−１００ＡＳ、芳香族系石油樹脂としては、ＪＸ日鉱日石エネルギー社製ネオポリマーＬ−９０、ネオポリマー１２０、ネオポリマー１３０、ネオポリマー１４０、ネオポリマー１５０、ネオポリマー１７０Ｓ、ネオポリマー１６０、ネオポリマーＥ−１００、ネオポリマーＥ−１３０、ネオポリマー１３０Ｓ、ネオポリマーＳ、東ソー社製ペトコールＬＸ、ペトコールＬＸ−ＨＳ、ペトコール１００Ｔ、ペトコール１２０、ペトコール１２０ＨＳ、ペトコール１３０、ペトコール１４０、ペトコール１４０ＨＭ、ペトコール１４０ＨＭ５、ペトコール１５０、ペトコール１５０ＡＳ、共重合系石油樹脂としては、日本ゼオン社製クイントンＤ１００、クイントンＮ１８０、クイントンＰ１９５Ｎ、クイントンＳ１００、クイントンＳ１９５、クイントンＵ１８５、クイントンＧ１００Ｂ、クイントンＧ１１５、クイントンＤ２００、クイントンＥ２００ＳＮ、クイントンＮ２９５、東ソー社製ペトロタック６０、ペトロタック７０、ペトロタック９０、ペトロタック１００、ペトロタック１００Ｖ、ペトロタック９０ＨＭ、ＤＣＰＤ系石油樹脂としては、丸善石油化学社製マルカレッツＭ−８９０Ａ、マルカレッツＭ−８４５Ａ、日本ゼオン社製クイントン１３２５、クイントン１３４５、クイントン１５００、クイントン１５２５Ｌ、クイントン１７００等が挙げられる。 Commercially available petroleum resins can be used as appropriate, and examples of aliphatic petroleum resins include quinton A100, quinton B170, quinton K100, quinton M100, quinton R100, quinton C200S, and Maruzen Petrochemicals manufactured by ZEON Corporation. Marcaretz T-100AS, Marcaretz R-100AS, and Aromatic Petroleum Resin made by JX Nippon Oil & Energy Co., Ltd. Neopolymer L-90, Neopolymer 120, Neopolymer 130, Neopolymer 140, Neopolymer 150, Neo Polymer 170S, Neopolymer 160, Neopolymer E-100, Neopolymer E-130, Neopolymer 130S, Neopolymer S, Tosoh Petcole LX, Petocol LX-HS, Petocol 100T, Petocol 120, Petco 120HS, Petol 130, Petol 140, Petol 140HM, Petol 140HM5, Petol 150, Petol 150AS, copolymer petroleum resins include ZEON Corporation Quinton D100, Quinton N180, Quinton P195N, Quinton S100, Quinton S195, Quinton S185, Quinton G100B, Quinton G115, Quinton D200, Quinton E200SN, Quinton N295, Tosoh PetroTac 60, PetroTac 70, PetroTac 90, PetroTac 100V, PetroTac 90HM, DCPD petroleum resin Petrochemicals Marcaretz M-890A, Marcaretz M-845A, Nippon Zeon Quinton 1325, Qui Ton 1345, Quinton 1500, Quinton 1525L, Quinton 1700, and the like.
また、本発明では、ロジン変性フェノール樹脂（Ａ）の分子量を大きくするために、ポリオール（ｄ）を使用することが出来る。ポリオール（ｄ）の水酸基はロジン類（ａ）のカルボン酸とエステル化反応し、高分子量化する。ポリオール（ｄ）はポリオール（ｄ）中の水酸基がロジン類（ａ）中のカルボン酸基１モルに対して０．１〜１．５モル、好ましくは０．３〜１．２モルの範囲が反応制御上好ましい。 In the present invention, the polyol (d) can be used to increase the molecular weight of the rosin-modified phenolic resin (A). The hydroxyl group of the polyol (d) undergoes an esterification reaction with the carboxylic acid of the rosin (a) to increase the molecular weight. The polyol (d) has a hydroxyl group in the polyol (d) in the range of 0.1 to 1.5 mol, preferably 0.3 to 1.2 mol, based on 1 mol of the carboxylic acid group in the rosin (a). It is preferable for reaction control.
ポリオール（ｄ）としては、特に限定されないが、２価アルコールとして、直鎖状アルキレン２価アルコールである１，２−エタンジオール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，４−ブタンジオール、１，２−ペンタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，２−ヘキサンジオール、１，５−ヘキサンジオール、２，５−ヘキサンジオール、１，７−ヘプタンジオール、１，８−オクタンジオール、１，２−オクタンジオール、１，９−ノナンジオール、１，２−デカンジオール、１，１０−デカンジオール、１，１２−ドデカンジオール、１，２−ドデカンジオール、１，１４−テトラデカンジオール、１，２−テトラデカンジオール、１，１６−ヘキサデカンジオール、１，２−ヘキサデカンジオール等が、分岐状アルキレン２価アルコールである２−メチル−２，４−ペンタンジオール、３−メチル−１，５−ペンタンジオール、２−メチル−２−プロピル−１，３−プロパンジオール、２，４−ジメチル−２，４−ジメチルペンタンジオール、２，２−ジエチル−１，３−プロパンジオ−ル、２，２，４−トリメチル−１，３−ペンタンジオール、ジメチロールオクタン、２−エチル−１，３−ヘキサンジオール、２，５−ジメチル−２，５−ヘキサンジオール、２−メチル−１，８−オクタンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、２，４−ジエチル−１，５−ペンタンジオール等が、環状アルキレン２価アルコールである１，２−シクロヘキサンジオール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノール、１，２−シクロヘプタンジオール、トリシクロデカンジメタノール、水添カテコール、水添レゾルシン、水添ハイドロキノン等、さらにポリエチレングリコール（ｎ＝２〜２０）、ポリプロピレングリコール（ｎ＝２〜２０）、ポリテトラメチレングリコール（ｎ＝２〜２０）等のポリエーテルポリオール、ポリエステルポリオール等を例示することができる。 The polyol (d) is not particularly limited, but as the dihydric alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2 which are linear alkylene dihydric alcohols are used. -Butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecane Diol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hex Decanediol, 1,2-hexadecanediol and the like are branched alkylene dihydric alcohols such as 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl- 1,3-propanediol, 2,4-dimethyl-2,4-dimethylpentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol Dimethyloloctane, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1, 1,2-cyclohexanediol in which 3-propanediol, 2,4-diethyl-1,5-pentanediol and the like are cyclic alkylene dihydric alcohols 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecane dimethanol, hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone, and the like, and polyethylene glycol (n = 2 to 2) 20), polyether polyols such as polypropylene glycol (n = 2 to 20) and polytetramethylene glycol (n = 2 to 20), polyester polyols, and the like.
さらに、３価以上のアルコールとしては、グリセリン、トリメチロ−ルプロパン、ペンタエリスリトール、１，２，６−ヘキサントリオール、３−メチルペンタン−１，３，５−トリオール、ヒドロキシメチルヘキサンジオール、トリメチロールオクタン、ジグリセリン、ジトリメチロ−ルプロパン、ジペンタエリスリト−ル、ソルビトール、イノシトール、トリペンタエリスリトール等が例示される。 Furthermore, as trihydric or higher alcohol, glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, Examples include diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol, tripentaerythritol and the like.
上記エステル化反応は、常法に従って行うことができる。通常１５０℃から３００℃の範囲で行われるが、使用する化合物の沸点および反応性を考慮して決定することができる。 The esterification reaction can be performed according to a conventional method. Usually, it is carried out in the range of 150 ° C. to 300 ° C., but can be determined in consideration of the boiling point and reactivity of the compound used.
本発明でのロジン変性フェノール樹脂（Ａ）は、重量固形分比で、ロジン類（ａ）５〜７５重量％が好ましく、レゾール型フェノール樹脂（ｂ）１５〜８５重量％が好ましい。ロジン類（ａ）が５重量％未満で、レゾール型フェノール樹脂（ｂ）が８５重量％を上回ると、ゲル化し易くなり反応制御が困難となる。また、ロジン類（ａ）が７５重量％を上回り、レゾール型フェノール樹脂（ｂ）が１５重量％未満であると、インキに必要な粘度および弾性を得られなくなる。また、さらにより好ましくはロジン類（ａ）が２０〜４０重量％で、レゾール型フェノール樹脂（ｂ）が４０〜７０重量％である。ロジンの重量固形分比率を低くすることで、ロジンの産地による樹脂、インキ性状のブレが少なく、より効果を発現し易い。 The rosin-modified phenolic resin (A) in the present invention is preferably 5 to 75% by weight of rosins (a) and 15 to 85% by weight of resole-type phenolic resin (b) in terms of weight to solid content. If the rosin (a) is less than 5% by weight and the resol type phenolic resin (b) is more than 85% by weight, gelation tends to occur and reaction control becomes difficult. Further, when the rosin (a) exceeds 75% by weight and the resol type phenol resin (b) is less than 15% by weight, the viscosity and elasticity required for the ink cannot be obtained. Still more preferably, the rosin (a) is 20 to 40% by weight and the resol type phenol resin (b) is 40 to 70% by weight. By reducing the weight-solid content ratio of rosin, there is little blurring of resin and ink properties due to the rosin production area, and the effect is more easily manifested.
再生処理した植物油（ｃ）については、重量固形分比で５〜２５重量％が好ましく、より好ましくは７〜２５重量％である。５重量％未満であると、印刷物の光沢向上の効果が得られず、２５重量％を上回ると、インキに必要な粘度および弾性を得ることができない。 About the vegetable oil (c) which carried out the regeneration process, 5 to 25 weight% is preferable by weight solid content ratio, More preferably, it is 7 to 25 weight%. If it is less than 5% by weight, the effect of improving the gloss of the printed matter cannot be obtained, and if it exceeds 25% by weight, the viscosity and elasticity required for the ink cannot be obtained.
本発明では、インキの流動性を向上させるため、石油樹脂（ｅ）を使用することができる。本発明で使用される石油樹脂（ｅ）は、重量固形分比で５〜３０重量％が好ましく、より好ましくは７〜３０重量％である。５重量％未満であると、インキに十分な流動性が得られなくなり、３０重量％を上回ると、インキに必要な粘度および弾性を得ることができない。 In the present invention, petroleum resin (e) can be used to improve the fluidity of the ink. The petroleum resin (e) used in the present invention is preferably 5 to 30% by weight, more preferably 7 to 30% by weight in terms of weight to solid content. If it is less than 5% by weight, sufficient fluidity cannot be obtained in the ink, and if it exceeds 30% by weight, the viscosity and elasticity required for the ink cannot be obtained.
本発明のロジン変性フェノール樹脂の製造方法としては、例えば反応釜にロジン類（ａ）、再生処理した植物油（ｃ）、石油樹脂（e）を１２０〜２６０℃で加熱溶融し、そこにレゾール型フェノール樹脂（ｂ）を添加し、１８０〜３００℃で１〜３０時間反応させる。その後、酸触媒、必要に応じてポリオール（ｄ）を添加し、１５０〜３００℃で１〜３０時間ロジン類とエステル化反応させる方法や、ロジン類（ａ）、再生処理した植物油（ｃ）、石油樹脂（ｅ）を１２０〜２６０℃で加熱溶融し、酸触媒、必要に応じてポリオール（ｄ）を添加し、１５０〜３００℃で１〜３０時間ロジン類とエステル化反応させ、１８０〜２６０℃でレゾール型フェノール樹脂（ｂ）を添加し、１８０〜３００℃で１〜２０時間反応させる方法がある。 As a method for producing the rosin-modified phenolic resin of the present invention, for example, rosins (a), regenerated vegetable oil (c) and petroleum resin (e) are heated and melted at 120 to 260 ° C. in a reaction kettle, and resole type A phenol resin (b) is added and it is made to react at 180-300 degreeC for 1 to 30 hours. Thereafter, an acid catalyst, a method of adding a polyol (d) as necessary, and an esterification reaction with rosins at 150 to 300 ° C. for 1 to 30 hours, rosins (a), regenerated vegetable oil (c), Petroleum resin (e) is heated and melted at 120 to 260 ° C., an acid catalyst and, if necessary, polyol (d) are added, and esterified with rosins at 150 to 300 ° C. for 1 to 30 hours. There is a method in which the resol type phenol resin (b) is added at ℃ and reacted at 180 to 300 ℃ for 1 to 20 hours.
上記の方法によって得られたロジン変性フェノール樹脂（Ａ）の重量平均分子量は特に限定されないが、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）による重量平均分子量（ポリスチレン換算）は５，０００〜３００，０００程度のものが好ましく、より好ましくは１０，０００〜１５０，０００である。５，０００未満であるとインキの粘度が低く、ミスチング等が発生し易くなり、３００，０００以上であると樹脂の溶解性が悪くなる為、インキの流動性が劣化し、光沢等が悪くなる。樹脂の溶解性については、０号ソルベントH（ＪＸ日鉱日石エネルギー社製）を用い、樹脂／０号ソルベントH＝２ｇ／１８ｇを２００℃で加熱溶解させ、温度を徐々に下げ、白濁する温度を測定する。白濁する温度が低い方が樹脂と溶剤の相溶性が良好であり、３０〜１７０℃程度のものが好ましい。 The weight average molecular weight of the rosin modified phenolic resin (A) obtained by the above method is not particularly limited, but the weight average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC) is about 5,000 to 300,000. Those are preferable, and more preferably 10,000 to 150,000. If it is less than 5,000, the viscosity of the ink is low and misting is likely to occur, and if it is 300,000 or more, the solubility of the resin is deteriorated, so that the fluidity of the ink is deteriorated and the gloss is deteriorated. . Regarding the solubility of the resin, No. 0 Solvent H (manufactured by JX Nippon Oil & Energy Co., Ltd.) is used, and the resin / No. 0 Solvent H = 2g / 18g is heated and dissolved at 200 ° C., and the temperature is gradually lowered to become cloudy. Measure. The lower the temperature at which white turbidity is, the better the compatibility between the resin and the solvent is, and a temperature of about 30 to 170 ° C. is preferred.
こうして得られたロジン変性フェノール樹脂（Ａ）に、必要に応じて植物油類、インキ用石油系溶剤、ゲル化剤を加えて加熱溶解させて平版印刷インキ用ワニスを製造することができる。 To the rosin-modified phenol resin (A) thus obtained, vegetable oils, petroleum-based solvents for ink, and gelling agents can be added and dissolved by heating, if necessary, to produce a lithographic printing ink varnish.
平版印刷インキ用ワニスに用いられる植物油類としては、各種公知のものを限定無く使用することができる。具体的には例えば、亜麻仁油、桐油、大豆油、サフラワー油、脱水ひまし油、または、これら植物油の熱重合油、酸化重合油がある。また、亜麻仁油脂肪酸メチル、大豆油脂肪酸メチル、亜麻仁油脂肪酸エチル、大豆油脂肪酸エチル、亜麻仁油脂肪酸プロピル、大豆油脂肪酸プロピル、亜麻仁油脂肪酸ブチル、大豆油脂肪酸ブチル、亜麻仁油脂肪酸イソブチル、大豆油脂肪酸イソブチル等といった、前述の植物油類のモノエステルが上げられる。これらは単独で用いても２種類以上を適宜併用しても良い。さらに、前述の再生処理した植物油（ｃ）を植物油類として使用することができる。 Various known oils can be used without limitation as vegetable oils used in lithographic printing ink varnishes. Specific examples include linseed oil, tung oil, soybean oil, safflower oil, dehydrated castor oil, or heat-polymerized oil and oxidized polymerized oil of these vegetable oils. Linseed oil fatty acid methyl, soybean oil fatty acid methyl, linseed oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl, linseed oil fatty acid isobutyl, soybean oil fatty acid Monoesters of the aforementioned vegetable oils such as isobutyl can be raised. These may be used alone or in combination of two or more. Furthermore, the above-mentioned regenerated vegetable oil (c) can be used as vegetable oils.
平版印刷インキ用ワニスに用いられる平版印刷インキ用石油系溶剤としては、従来公知の印刷インキ用溶剤を特に限定無く使用することができる。具体的には例えば、ＪＸ日鉱日石エネルギー社製の０号ソルベント、４号ソルベント、５号ソルベント、６号ソルベント、７号ソルベント、ＡＦソルベント4号、ＡＦソルベント５号、ＡＦソルベント６号、ＡＦソルベント７号等があげられる。これらは単独で用いても、２種類以上を適宜併用しても良い。特に環境対策として、芳香族炭化水素の含有率が１重量％以下であるアロマフリーソルベントを使用することが好ましい。 As the petroleum solvent for lithographic printing ink used in the lithographic printing ink varnish, a conventionally known printing ink solvent can be used without any particular limitation. Specifically, for example, No. 0 Solvent, No. 4 Solvent, No. 5 Solvent, No. 6 Solvent, No. 7 Solvent, AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, AF, manufactured by JX Nippon Oil & Energy Corporation, AF Solvent 7 etc. are mention | raise | lifted. These may be used alone or in combination of two or more. In particular, as an environmental measure, it is preferable to use an aroma-free solvent having an aromatic hydrocarbon content of 1% by weight or less.
前記ゲル化剤としては、例えば、オクチル酸アルミニウム、ステアリン酸アルミニウム、アルミニウムトリイソプロポキシド、アルミニウムトリブトキシド、アルミニウムジプロポキシドモノアセチルアセテート、アルミニウムジブトキシドモノアセチルアセテート、アルミニウムトリアセチルアセテートなどの各種公知な物を使用できる。 Examples of the gelling agent include various known materials such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, and aluminum triacetyl acetate. Can be used.
平版印刷インキ用ワニスのロジン変性フェノール樹脂（Ａ）、植物油類、石油系溶剤、ゲル化剤の組成比率としては、用途に応じて適宜それぞれ適宜決定すればよいが、通常ロジン変性フェノール樹脂の割合は５〜６０重量％程度、植物油類の割合は、０〜８０重量％程度、石油系溶剤の割合は、０〜８０重量％程度、ゲル化剤の割合は０〜４重量％程度、好ましくは０〜３％程度である。また、本発明以外の方法により製造したロジン変性フェノール樹脂や、石油樹脂等を併用することもできる。 The composition ratio of the rosin-modified phenolic resin (A), vegetable oil, petroleum-based solvent, and gelling agent in the varnish for lithographic printing ink may be appropriately determined depending on the use. Is about 5 to 60% by weight, the proportion of vegetable oil is about 0 to 80% by weight, the proportion of petroleum solvent is about 0 to 80% by weight, the proportion of gelling agent is about 0 to 4% by weight, preferably It is about 0 to 3%. In addition, rosin-modified phenolic resins produced by methods other than the present invention, petroleum resins and the like can be used in combination.
この平版印刷インキワニス、顔料、石油系溶剤および添加剤により平版印刷インキが製造される。本発明で使用される顔料としては、酸化チタンなどの白顔料、ミネラルファーネスイエロー、ネーブルスイエロー、ナフトールイエローＳ，ハンザイエローＧ，キノリンイエローレーキ、パーマネントイエローＮＣＧ，タートラジンレーキなどの黄顔料、インダスレンブリリアントオレンジＲＫ、ピラゾンオレンジ、バルカンオレンジ、ベンジジンオレンジＧ、インダスレンブリリアントオレンジＧＫなどの橙色顔料、パーマネントレッド４Ｒ、リオノールレッド、ピラロゾンレッド、ウオッチングレッツドカルシウム塩、レーキレッドＤ，ブリリアントカーミン６Ｂ、エオシンレーキ、ローダミンレーキＢ、アリザリンレーキ、ブリリアントカーミン３Ｂなどの赤色顔料、ファーストバイオレットＢ、メチルバイオレットレーキなどの紫色顔料、紺青、コバルトブルー、アルカリブルーレーキ、ビクトリアブルーレーキ、フタロシアニンブルー、無金属フタロシアニンブルー、フタロシアニンブルー部分塩素化物、ファーストスカイブルー、インダスレンブルーＢＣなどの青色顔料、ピグメントグリーンＢ、マラカイドグリーンレーキ、ファイナスイエリーグリーンＧなどの緑色顔料、カーボンブラック、アセチレンブラック、ランブラック、アニリンブラックなどの黒色顔料などが挙げられる。 A lithographic printing ink is produced from the lithographic printing varnish, pigment, petroleum solvent and additives. Examples of pigments used in the present invention include white pigments such as titanium oxide, yellow pigments such as mineral furnace yellow, navel yellow, naphthol yellow S, hansa yellow G, quinoline yellow lake, permanent yellow NCG, tartrazine lake, and indus. Orange pigments such as Rembrilliant Orange RK, Pirazone Orange, Vulcan Orange, Benzidine Orange G, Indus Len Brilliant Orange GK, Permanent Red 4R, Lionol Red, Pyrarozone Red, Watching Lettuce Calcium Salt, Lake Red D, Brilliant Carmine 6B , Red pigments such as eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B, purple such as first violet B, methyl violet lake Paint, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, indanthrene blue BC and other blue pigments, pigment green B, malachide green lake And green pigments such as FINA SWIRY GREEN G, and black pigments such as carbon black, acetylene black, lan black, and aniline black.
また、平版印刷インキ中への、その他添加剤として、耐摩擦、ブロッキング防止、スベリ、スリキズ防止を目的とする各種添加剤を使用することができ、必要に応じて、レベリング剤、帯電防止剤、界面活性剤、消泡剤、等を添加してもよい。 Also, as other additives in the lithographic printing ink, various additives for the purpose of anti-friction, anti-blocking, slip, anti-scratch can be used, leveling agents, antistatic agents, A surfactant, an antifoaming agent, etc. may be added.
本発明の平版印刷インキの組成の一例としては、
・本発明により製造されるロジン変フェノール樹脂（Ａ） ５〜６０重量％
・植物油類（再生処理した植物油（ｃ）を含む） ０〜８０重量％
・石油系溶剤 ０〜８０重量％
・ゲル化剤 ０〜４重量％
・顔料 ５〜４０重量％ ・その他の樹脂 ０〜４０重量％
・その他添加剤 １〜５重量％
などが好ましい組成として挙げられる。その他の樹脂とは、一般的に平版印刷インキ組成物に用いられるロジン変性フェノール樹脂あるいは石油系樹脂あるいはアルキッド樹脂を表す。ＶＯＣフリータイプのインキとして使用する際には、上記組成において、石油系溶剤を０重量％とする。この際、必要に応じて脂肪酸モノエステル化合物を０〜６０重量％含有しても差し支えない。
As an example of the composition of the lithographic printing ink of the present invention,
-Rosin modified phenolic resin (A) produced by the present invention 5-60 wt%
・ Vegetable oils (including regenerated vegetable oil (c)) 0-80% by weight
・ Petroleum solvent 0-80% by weight
-Gelling agent 0-4% by weight
・ Pigment 5-40% by weight ・ Other resins 0-40% by weight
・ Other additives 1 to 5% by weight
Etc. are mentioned as preferred compositions. The other resin represents a rosin-modified phenol resin, a petroleum resin, or an alkyd resin generally used for a lithographic printing ink composition. When used as a VOC-free type ink, the petroleum solvent is 0% by weight in the above composition. At this time, the fatty acid monoester compound may be contained in an amount of 0 to 60% by weight as necessary.
以下に、実施例により本発明をさらに詳細に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。なお、本発明において、特に断らない限り、「部」は、「重量部」を表し、「％」は「重量％」を表す。また、本発明において、重量平均分子量は、東ソー(株)製ゲルパーミネイションクロマトグラフィ（ＨＬＣ−８２２０。）で測定した。検量線は標準ポリスチレンサンプルにより作成した。溶離液はテトラヒドロフランを、カラムにはＴＳＫｇｅｌ ＳｕｐｅｒＨＭ−Ｍ（東ソー(株)製）３本を用いた。測定は流速０．６ｍｌ／分、注入量１０μｌ、カラム温度４０℃で行った。さらに、本発明において、特に断らない限り、「分子量」とは、重量平均分子量を示す。 The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the present invention, “part” represents “part by weight” and “%” represents “% by weight” unless otherwise specified. In the present invention, the weight average molecular weight was measured by gel permeation chromatography (HLC-8220) manufactured by Tosoh Corporation. A calibration curve was prepared with a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C. Furthermore, in the present invention, “molecular weight” means a weight average molecular weight unless otherwise specified.
（レゾール型フェノール樹脂の合成例１）
撹拌機、冷却器、温度計をつけた４つ口フラスコにオクチルフェノール１０００部、９２％パラホルムアルデヒド３５０部、９８％水酸化カルシウム１０部、キシレン４８０部を加えて、９０℃で５時間反応させる。その後キシレン４００部、水道水２５０部を加え、９８％硫酸を１０部滴下した。撹拌、静置後、上層部を取り出し、不揮発分６０％のレゾール型フェノール樹脂のキシレン溶液を得て、これをレゾール液Ａとした。
(Synthesis example 1 of resol type phenol resin)
To a four-necked flask equipped with a stirrer, a cooler and a thermometer, 1000 parts of octylphenol, 350 parts of 92% paraformaldehyde, 10 parts of 98% calcium hydroxide and 480 parts of xylene are added and reacted at 90 ° C. for 5 hours. Thereafter, 400 parts of xylene and 250 parts of tap water were added, and 10 parts of 98% sulfuric acid was added dropwise. After stirring and allowing to stand, the upper layer portion was taken out to obtain a xylene solution of a resol type phenol resin having a nonvolatile content of 60%.
（レゾール型フェノール樹脂の合成例２）
撹拌機、冷却器、温度計をつけた４つ口フラスコにブチルフェノール１０００部、９２％パラホルムアルデヒド４８０部、９８％水酸化カルシウム１０部、キシレン５３０部を加えて、９０℃で５時間反応させる。その後キシレン４３０部、水道水２５０部を加え、９８％硫酸を１０部滴下した。撹拌、静置後、上層部を取り出し、不揮発分６０％のレゾール型フェノール樹脂のキシレン溶液を得て、これをレゾール液Ｂとした。
(Synthesis example 2 of resol type phenol resin)
To a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 1000 parts of butylphenol, 480 parts of 92% paraformaldehyde, 10 parts of 98% calcium hydroxide, and 530 parts of xylene are added and reacted at 90 ° C. for 5 hours. Thereafter, 430 parts of xylene and 250 parts of tap water were added, and 10 parts of 98% sulfuric acid was added dropwise. After stirring and allowing to stand, the upper layer portion was taken out to obtain a xylene solution of a resol type phenol resin having a non-volatile content of 60%.
（レゾール型フェノール樹脂の合成例３）
撹拌機、冷却器、温度計をつけた４つ口フラスコにオクチルフェノール６６１部、ブチルフェノール９０８部、９２％パラホルムアルデヒド６３２部、９８％水酸化カルシウム１５．７部、キシレン７９５部を加えて、９０℃で５時間反応させる。その後キシレン６３８部、水道水８３部を加え、９８％硫酸を１６．６部滴下した。撹拌、静置後、上層部を取り出し、不揮発分６０％のレゾール型フェノール樹脂のキシレン溶液を得て、これをレゾール液Ｃとした。
(Synthesis example 3 of resol type phenol resin)
To a four-necked flask equipped with a stirrer, a condenser, and a thermometer, 661 parts of octylphenol, 908 parts of butylphenol, 632 parts of 92% paraformaldehyde, 15.7 parts of 98% calcium hydroxide, and 795 parts of xylene were added, and 90 ° C. For 5 hours. Thereafter, 638 parts of xylene and 83 parts of tap water were added, and 16.6 parts of 98% sulfuric acid was added dropwise. After stirring and standing, the upper layer portion was taken out to obtain a xylene solution of a resol type phenol resin having a non-volatile content of 60%.
（樹脂合成の実施例１）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油５０部、石油樹脂「ペトコール１２０（商品名）」（東ソー（株）製：重量平均分子量１７００）２４０部を添加した。レゾール液Ａ６５０部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸０．０８部、グリセリン１０部を仕込み８時間反応させた。重量平均分子量（Ｍｗ）７６０００、酸価７の樹脂１を得た。
(Example 1 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, and 50 parts of recycled vegetable oil manufactured by Marusho Co., Ltd. 120 parts of “120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) was added. After adding 650 parts of resole liquid A (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 0.08 parts of p-toluenesulfonic acid and 10 parts of glycerin were added at 250 ° C. The preparation was allowed to react for 8 hours. A resin 1 having a weight average molecular weight (Mw) of 76000 and an acid value of 7 was obtained.
（樹脂合成の実施例２）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油２５部を添加した。レゾール液Ｂ１１２．５部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸０．０８部、グリセリン１２．５部を仕込み８時間反応させた。重量平均分子量（Ｍｗ）８６０００、酸価１６の樹脂２を得た。
(Example 2 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, and 25 parts of recycled vegetable oil manufactured by Marusho Co., Ltd. was added. After adding 112.5 parts of resol solution B (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 0.08 parts of p-toluenesulfonic acid and glycerin 12 were added at 250 ° C. .5 parts was charged and reacted for 8 hours. A resin 2 having a weight average molecular weight (Mw) of 86000 and an acid value of 16 was obtained.
（樹脂合成の実施例３）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油６２．５部を添加した。レゾール液Ａ７５部を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸０．０８部、グリセリン１２．５部を仕込み８時間反応させた。重量平均分子量（Ｍｗ）８８０００、酸価１８の樹脂３を得た。
(Example 3 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, and 62.5 parts of Marusho Regenerated vegetable oil was added. . 75 parts of resole liquid A was added dropwise at 200 ° C. over 5 hours, and then the temperature was raised to 250 ° C. while removing xylene. At 250 ° C., 0.08 parts of p-toluenesulfonic acid and 12.5 parts of glycerin were added and reacted for 8 hours. I let you. A resin 3 having a weight average molecular weight (Mw) of 88000 and an acid value of 18 was obtained.
（樹脂合成の実施例４）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油２５部、石油樹脂「ペトコール１２０（商品名）」（東ソー（株）製：重量平均分子量１７００）１２．５部を添加した。レゾール液Ｃ１００部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸０．０８部、グリセリン１２．５部を仕込み８時間反応させた。重量平均分子量（Ｍｗ）４８０００、酸価１６の樹脂４を得た。
(Example 4 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, and 25 parts of recycled vegetable oil manufactured by Marusho Co., Ltd. 12.5 parts of “120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) was added. After 100 parts of resole liquid C (solid content 60%) was added dropwise at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 0.08 parts of p-toluenesulfonic acid and glycerin 12.5 at 250 ° C. The parts were charged and allowed to react for 8 hours. A resin 4 having a weight average molecular weight (Mw) of 48000 and an acid value of 16 was obtained.
（樹脂合成の実施例５）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油２６．３部、石油樹脂「ペトコール１２０（商品名）」（東ソー（株）製：重量平均分子量１７００）３９．５部を添加した。レゾール液Ｃ８４．２部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸０．０８部、グリセリン１３．２部を仕込み８時間反応させた。重量平均分子量（Ｍｗ）５００００、酸価１８の樹脂５を得た。
(Example 5 of resin synthesis)
In a four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, and 26.3 parts of recycled vegetable oil manufactured by Marusho Co., Ltd., petroleum resin 39.5 parts of “Petocol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) was added. 84.2 parts (60% solids) of resole liquid C was added dropwise at 200 ° C. over 5 hours, and then the temperature was raised to 250 ° C. while removing xylene, and 0.08 parts of p-toluenesulfonic acid and glycerin 13 were added at 250 ° C. 2 parts were charged and reacted for 8 hours. A resin 5 having a weight average molecular weight (Mw) of 50000 and an acid value of 18 was obtained.
（樹脂合成の実施例６）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油２７．８部、石油樹脂「ペトコール１２０（商品名）」（東ソー（株）製：重量平均分子量１７００）８３．３部を添加した。レゾール液Ｃ５５．６部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸０．５部、グリセリン１１．１部を仕込み１４時間反応させた。重量平均分子量（Ｍｗ）５２０００、酸価１４の樹脂６を得た。
(Example 6 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, 27.8 parts of Marusho's regenerated vegetable oil, petroleum resin 83.3 parts of “Petocol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) was added. After 55.6 parts of resole liquid C (solid content 60%) was added dropwise at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and at 250 ° C., 0.5 parts of p-toluenesulfonic acid, glycerin 11 1 part was charged and reacted for 14 hours. A resin 6 having a weight average molecular weight (Mw) of 52,000 and an acid value of 14 was obtained.
（樹脂合成の実施例７）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油６．７部を添加した。レゾール液Ｃ２０部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸０．０８部、グリセリン６．７部を仕込み１６時間反応させた。重量平均分子量（Ｍｗ）４２０００、酸価１１の樹脂７を得た。
(Example 7 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, and 6.7 parts of Marusho's regenerated vegetable oil was added. . After adding 20 parts of Resol liquid C (solid content: 60%) dropwise at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and at 250 ° C., 0.08 parts of p-toluenesulfonic acid and glycerin 6.7 were added. The parts were charged and allowed to react for 16 hours. A resin 7 having a weight average molecular weight (Mw) of 42,000 and an acid value of 11 was obtained.
（樹脂合成の実施例８）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油２０部、石油樹脂「ペトコール１２０（商品名）」（東ソー（株）製：重量平均分子量１７００）３０部を添加した。レゾール液Ａ４０部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸０．５部、ペンタエリスリトール１０部を仕込み１３時間反応させた。重量平均分子量（Ｍｗ）６４０００、酸価１３の樹脂８を得た。
(Example 8 of resin synthesis)
In a four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas. 120 parts (trade name) "(manufactured by Tosoh Corporation: weight average molecular weight 1700) was added. After 40 parts of resole liquid A (60% solid content) was added dropwise at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, 0.5 parts of p-toluenesulfonic acid and 10 parts of pentaerythritol at 250 ° C. Was allowed to react for 13 hours. A resin 8 having a weight average molecular weight (Mw) of 64000 and an acid value of 13 was obtained.
（樹脂合成の比較例Ａ）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、レゾール液Ａ４６．９部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でグリセリン９．４部を仕込み１４時間反応させた。重量平均分子量（Ｍｗ）７２０００、酸価１８の樹脂Ａを得た。
(Comparative example A of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, and 46.9 parts of resole liquid A (solid content 60%) was 200. After dropping at 5 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 9.4 parts of glycerin was charged at 250 ° C. and reacted for 14 hours. A resin A having a weight average molecular weight (Mw) of 72,000 and an acid value of 18 was obtained.
（樹脂合成の比較例Ｂ）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、レゾール液Ｂ６２．１部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸、グリセリン１０．３部を仕込み１３時間反応させた。重量平均分子量（Ｍｗ）６６０００、酸価１７の樹脂Ｂを得た。
(Comparative Example B for Resin Synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin were dissolved at 200 ° C. while blowing nitrogen gas, and 62.1 parts of resole liquid B (solid content 60%) were 200 parts. After dropping at 5 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene. A resin B having a weight average molecular weight (Mw) of 66000 and an acid value of 17 was obtained.
（樹脂合成の比較例Ｃ）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、石油樹脂「ペトコール１２０Ｔ（商品名）」（東ソー（株）製：重量平均分子量１７００）を１９．２部添加した。レゾール液Ｃ６１．５部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でｐ−トルエンスルホン酸、グリセリン１１．５部を仕込み１６時間反応させた。重量平均分子量（Ｍｗ）８８０００、酸価１７の樹脂Ｃを得た。
(Comparative Example C of Resin Synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas, and the petroleum resin “Petocol 120T (trade name)” (Tosoh Corporation) 19.2 parts of a weight average molecular weight 1700) was added. 61.5 parts (60% solids) of resole liquid C was added dropwise at 200 ° C. over 5 hours, and then the temperature was raised to 250 ° C. while removing xylene, and 11.5 parts of p-toluenesulfonic acid and glycerin were added at 250 ° C. The preparation was allowed to react for 16 hours. A resin C having a weight average molecular weight (Mw) of 88000 and an acid value of 17 was obtained.
（樹脂合成の比較例Ｄ）
撹拌機、水分離器付き冷却器、温度計をつけた４つ口フラスコに、ガムロジン１００部を窒素ガスを吹き込みながら２００℃で溶解し、（株）丸正製再生植物油２０部、石油樹脂「ペトコール１２０Ｔ（商品名）」（東ソー（株）製：重量平均分子量１７００）を２０部添加した。レゾール液Ｃ５０部（固形分６０％）を２００℃で５時間かけて滴下後、キシレンを除去しながら２５０℃に昇温させ、２５０℃でグリセリン１０部を仕込み１６時間反応させた。重量平均分子量（Ｍｗ）７４０００、酸価１３の樹脂Ｃを得た。
(Comparative Example D of Resin Synthesis)
In a four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer, 100 parts of gum rosin was dissolved at 200 ° C. while blowing nitrogen gas. 20 parts of “120T (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) was added. After 50 parts of resole liquid C (solid content 60%) was added dropwise at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 10 parts of glycerin was added at 250 ° C. and reacted for 16 hours. A resin C having a weight average molecular weight (Mw) of 74000 and an acid value of 13 was obtained.
樹脂合成の実施例１〜８、比較例Ａ〜Ｄの樹脂のロジン変性フェノール樹脂の固形分重量％での配合組成、並びに樹脂の性状である重量平均分子量および、酸価を表１に示す。 Table 1 shows the blending composition of the resins of Examples 1 to 8 and Comparative Examples A to D in terms of solid content by weight of the rosin-modified phenol resin, and the weight average molecular weight and the acid value which are the properties of the resin.
＜ワニスの実施例、比較例＞
撹拌機、水分離器付還流冷却器、温度計付き４つ口フラスコに、それぞれ、樹脂合成の実施例１〜８および比較例Ａ〜Ｄで得られたロジン変性フェノール樹脂（樹脂１〜８、樹脂Ａ〜Ｄ）、大豆油、石油系溶剤（ＪＸ日鉱日石エネルギー社製ＡＦソルベント７）、ゲル化剤（川研ファインケミカル（株）製ＡＬＣＨ）を表２のような配合組成で仕込み、窒素ガスを吹き込みながら１９０℃にて１時間加熱撹拌してワニス（ワニス１〜８、ワニスＡ〜Ｄ）を製造した。
<Examples of varnish, comparative example>
To a stirrer, a reflux condenser with a water separator, and a four-neck flask with a thermometer, the rosin-modified phenol resins (resins 1 to 8, Resin 1 to 8, Resins A to D), soybean oil, petroleum-based solvent (AF solvent 7 manufactured by JX Nippon Oil & Energy Corporation), gelling agent (ALCH manufactured by Kawaken Fine Chemical Co., Ltd.) with the composition shown in Table 2, and nitrogen While blowing gas, the mixture was heated and stirred at 190 ° C. for 1 hour to produce varnishes (varnishes 1 to 8, varnishes A to D).
＜平版印刷インキの実施例、比較例＞
前記方法で得られたワニス１〜８、ワニスＡ〜Ｄのそれぞれと、カーボン顔料三菱カーボンＭＡ７（三菱化学製）と、石油系溶剤（ＪＸ日鉱日石エネルギー社製ＡＦソルベント７）とを、表３の配合組成にて、常法に従い三本ロールを用いて練肉分散し、実施例１〜８、比較例Ａ〜Ｄのインキを得た。
<Examples of lithographic printing ink, comparative examples>
Each of varnishes 1 to 8 and varnishes A to D obtained by the above method, carbon pigment Mitsubishi Carbon MA7 (manufactured by Mitsubishi Chemical), and petroleum solvent (AF solvent 7 manufactured by JX Nippon Oil & Energy Corporation) The mixture composition of No. 3 was kneaded and dispersed using three rolls according to a conventional method, and inks of Examples 1 to 8 and Comparative Examples A to D were obtained.
実施例および比較例で得られた平版印刷インキについて、下記の方法で光沢値、流動性、地汚れを評価した。評価結果を表４に示す。 The lithographic printing inks obtained in the examples and comparative examples were evaluated for gloss value, fluidity and background stain by the following methods. The evaluation results are shown in Table 4.
＜光沢値の評価＞
光沢値は、プルーフバウ展色機にて、三菱製紙社製パールコートに同一濃度に展色し、光沢計グロスメーターモデルＧＭ−２６（（株）村上色彩技術研究所製）にて６０°光沢を測定した。数値が高い程、光沢が良いことを表す。
（評価基準） ◎：６０以上、○：５０以上〜６０未満、×：５０未満
<Evaluation of gloss value>
Gloss value is 60% gloss with gloss meter gloss meter model GM-26 (manufactured by Murakami Color Research Laboratory Co., Ltd.) with proof bow color developing machine and the same density on pearl coat manufactured by Mitsubishi Paper Industries. Was measured. The higher the value, the better the gloss.
(Evaluation criteria) ◎: 60 or more, ○: 50 or more to less than 60, x: less than 50
＜流動性の測定方法＞
２．１ｃｃを半球状の窪みのついた金属板にインキを入れ、１５分間静置させた後、６０度に傾け１０分間で流れた長さを測定し、以下の評価基準に基づいて評価を行った。値が高いほどインキのしまりが少なく、流動性が良好であることを示す。
（評価基準） ◎：８０ｍｍ以上、○：７０ｍｍ以上〜８０ｍｍ未満、×：７０ｍｍ未満
<Measurement method of fluidity>
2.1 cc of ink is put on a metal plate with a hemispherical depression and left to stand for 15 minutes, then the length that flows in 10 minutes by tilting to 60 degrees is measured and evaluated based on the following evaluation criteria. went. Higher values indicate less ink tightness and better fluidity.
(Evaluation criteria) A: 80 mm or more, B: 70 mm or more and less than 80 mm, X: less than 70 mm
＜地汚れの評価＞
三菱ＢＴ２−８００ＮＥＯオフ輪印刷機（三菱重工社製）にて８００ｒｐｍで用紙をＮＰＩコート紙６６．５ｋｇ（日本製紙社製）として各インキ２万枚の印刷試験を行い、印刷時の地汚れを比較した。湿し水はアクワマジックＮＳ（東洋インキ社製）１．５％の水道水を用いて行い、水巾の下限付近での印刷状態の比較を行うために、水巾の下限値よりも２％高い水ダイヤル値で印刷を行い、印刷紙面の汚れの有無の確認を行った。
<Evaluation of dirt>
Using a Mitsubishi BT2-800 NEO off-wheel printing machine (Mitsubishi Heavy Industries, Ltd.), a printing test was performed on 20,000 sheets of each ink using 800 rpm and NPI-coated paper at 66.5 kg (Nippon Paper Industries Co., Ltd.). Compared. The dampening solution is 1.5% tap water from AQUAMAG NS (Toyo Ink Co., Ltd.), and 2% of the lower limit of the water width is used to compare the printing conditions near the lower limit of the water width. Printing was performed with a high water dial value, and the presence or absence of smudges on the printing paper surface was checked.
表４の結果から明らかなように、再生植物油と反応させたロジン変性フェノール樹脂を用いたインキは、光沢が良好で、さらに石油樹脂を含有することで流動性に優れ、エステル化反応触媒に酸触媒を用いることで地汚れが軽減することが確認された。 As is apparent from the results in Table 4, the ink using the rosin-modified phenolic resin reacted with the regenerated vegetable oil has a good gloss and excellent fluidity by containing a petroleum resin. It was confirmed that background contamination was reduced by using a catalyst.
酸触媒下で反応してなるロジン変性フェノール樹脂を含有する印刷インキを使用することで、様々な条件下で印刷時の地汚れを軽減させ長時間安定した印刷が可能で、光沢感のある高品質の印刷物を得ることが出来る印刷インキ用組成物の合成方法並びにそれを用いたインキを提供することが可能となる。 By using printing ink containing rosin-modified phenolic resin that reacts in the presence of an acid catalyst, it is possible to reduce scumming during printing under various conditions, enabling stable printing for a long period of time, and high glossiness. It is possible to provide a method for synthesizing a printing ink composition capable of obtaining a quality printed matter, and an ink using the same.
Claims (7)
A printed matter obtained by printing the planographic printing ink according to claim 6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011260735A JP2013112757A (en) | 2011-11-29 | 2011-11-29 | Lithographic ink and printed matter |
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| JP2011260735A JP2013112757A (en) | 2011-11-29 | 2011-11-29 | Lithographic ink and printed matter |
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| JP2013112757A true JP2013112757A (en) | 2013-06-10 |
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| JP2011260735A Pending JP2013112757A (en) | 2011-11-29 | 2011-11-29 | Lithographic ink and printed matter |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2016208375A1 (en) * | 2015-06-24 | 2017-06-29 | Ｄｉｃグラフィックス株式会社 | Rosin-modified phenolic resin and printing ink |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2016208375A1 (en) * | 2015-06-24 | 2017-06-29 | Ｄｉｃグラフィックス株式会社 | Rosin-modified phenolic resin and printing ink |
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